JP3826395B2 - Impregnating composition for automotive and marine interior materials and method for producing automotive and marine interior materials - Google Patents

Description

【００５２】
【表２】

【００５３】
実施例１〜９、比較例１、２、及び表１、２において
Ｐ−ＭＤＩ（１） ：ポリメリックＭＤＩ
イソシアネート含量＝３１．０％
ＭＤＩ含有量＝３９％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝９８％
酸度＝０．００６％
Ｐ−ＭＤＩ（２） ：ポリメリックＭＤＩ
イソシアネート含量＝３１．５％
ＭＤＩ含有量＝４５％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝８７％
酸度＝０．００６％
Ｐ−ＭＤＩ（３） ：ポリメリックＭＤＩ
イソシアネート含量＝３１．０％
ＭＤＩ含有量＝４３％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝９６％
酸度＝０．０１０％
Ｐ−ＭＤＩ（４） ：ポリメリックＭＤＩ
イソシアネート含量＝２９．５％
ＭＤＩ含有量＝４３％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝９５％
酸度＝０．０１５％
Ｐ−ＭＤＩ（５） ：ポリメリックＭＤＩ
イソシアネート含量＝３１．０％
ＭＤＩ含有量＝３４％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝７５％
酸度＝０．００６％
Ｐ−ＭＤＩ（６） ：ポリメリックＭＤＩ
イソシアネート含量＝３０．１％
ＭＤＩ含有量＝２７％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝９９．５％
酸度＝０．００８％
Ｐ−ＭＤＩ（７） ：ポリメリックＭＤＩ
イソシアネート含量＝３０．２％
ＭＤＩ含有量＝３５％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝８６％
酸度＝０．００６％
Ｐ−ＭＤＩ（８） ：ポリメリックＭＤＩ
イソシアネート含量＝３１．０％
ＭＤＩ含有量＝４１％
ＭＤＩ中の４，４′−ＭＤＩ含有量＝９８．５％
酸度＝０．００６％
ＭＤＩ（１） ：ジフェニルメタンジイソシアネート
ＭＤＩ中の４，４′−ＭＤＩ含有量＝８１％
酸度＝０．００６％
ＭＤＩ（２） ：ジフェニルメタンジイソシアネート
ＭＤＩ中の４，４′−ＭＤＩ含有量＝７０％
酸度＝０．００６％
ＭＤＩ（３） ：ジフェニルメタンジイソシアネート
ＭＤＩ中の４，４′−ＭＤＩ含有量＝９９％
酸度＝０．００６％
１，３−ＢＤ ：１，３−ブタンジオール
ＥＤＡ ：エチレンジアミン
Ｋ−５４ ：イソシアヌレート化触媒
２，４，６−トリス（ジメチルアミノメチル）フェノール
エアプロダクツアンドケミカル製
ＲＡ−６００ ：イソシアヌレート化停止剤
酸性リン酸エステル、東邦化学工業製
ＳＺ−１６４２ ：シリコン系整泡剤、日本ユニカー製
Ｂ−８４５１ ：シリコン系整泡剤、ゴールドシュミット製
Ｌ−５３４０ ：シリコン系整泡剤、日本ユニカー製
ＴＳＦ−４５１ ：シリコン系消泡剤、ＧＥ東芝シリコーン製
ＫＦ−９６ ：シリコン系消泡剤、信越化学工業製
ＴＳＦ−４７５１ ：シリコン系消泡剤、ＧＥ東芝シリコーン製
ＫＦ−６００１ ：シリコン系消泡剤、信越化学工業製
ＤＢＴＤＬ ：ジブチルチンジラウレート
Ｕ−ＣＡＴ ＳＡ１：ＤＢＵのフェノ−ル塩、エアプロダクツアンドケミカル製
【００５４】
〔自動車用、船舶用内装材用含浸剤組成物の貯蔵安定性〕
得られた自動車用、船舶用内装材用含浸剤組成物を３０℃、−５℃にて１ヶ月保管したところ、実施例１〜９、比較例１、２で得られた全ての自動車用、船舶用内装材用含浸剤組成物の外観、粘度は変化が見られず、良好な結果であった。
【００５５】
〔自動車用、船舶用内装材の製造〕
自動車用、船舶用内装材製造時に噴霧する触媒には、ＴＥＤＡ Ｌ−３３（トリエチレンジアミンのジエチレングリコール溶液、エアプロダクツアンドケミカル製）を用いた。なお、プレス成形条件は以下の通り。
温度：１２０℃
時間：３０秒
圧力：１０ＭＰａ
【００５６】
実施例１０
軟質ポリウレタンスラブフォーム（密度：３０ｋｇ／ｍ³ 、長さ２００ｍｍ、幅１００ｍｍ、厚さ７ｍｍ）に、ＮＣＯ−１を含浸させて（含浸量：２．６ｇ）、触媒１．６ｇを噴霧し、プレス成形機にて成形した。結果を表３に示す。
【００５７】
実施例１１、１６、比較例３
ＮＣＯ−１の代わりにＮＣＯ−２、７、１０にする以外は、実施例１０と同様にして成形した。結果を表３、４に示す。
【００５８】
実施例１２
軟質ポリウレタンフォームのリボンデッドフォーム（密度：８０ｋｇ／ｍ³ 、長さ２００ｍｍ、幅１００ｍｍ、厚さ７ｍｍ）に、ＮＣＯ−３を含浸させて（含浸量：２．６ｇ）、水：触媒＝９：１（質量比）の混合液１．６ｇを噴霧し、プレス成形機にて成形した。結果を表３に示す。
【００５９】
実施例１３、１７、比較例４
ＮＣＯ−３の代わりにＮＣＯ−４、８、１１にする以外は、実施例１２と同様にして成形した。結果を表３、４に示す。
【００６０】
実施例１４
軟質ポリウレタンフォームのリボンデッドフォーム（密度：５０ｋｇ／ｍ³ 、長さ２００ｍｍ、幅１００ｍｍ、厚さ７ｍｍ）に、ＮＣＯ−５を含浸させて（含浸量：２．６ｇ）、水：触媒＝９：１（質量比）の混合液１．６ｇを噴霧した後、フォームの上部及び下部に不織布を当てて、プレス成形機にて成形した。結果を表３に示す。
【００６１】
実施例１５、１８
ＮＣＯ−５の代わりにＮＣＯ−６、９にする以外は、実施例１４と同様にして成形した。結果を表３、４に示す。
【００６２】
【表３】

【００６３】
【表４】

【００６４】
表３、４において
・反応性：成形直後成形物のたわみ具合を目視で評価。
１：成形物からイソシアネートがしみ出している。
２：成形物が柔らかく大きくたわむ。
３：成形物に硬さはあるがたわむ。
４：成形物は硬くたわみも少ない。
５：成形物は硬くたわまない。
・成形性：成形後の成形物のらくがん性の有無で評価。
○：無、△：僅かにある、×：有
・外観：成形後成形物からのイソシアネートのしみ出しの有無で評価。
○：無、△：僅かにある、×：有
・初期硬度：成形後成形物を指で押し、つぶれ具合で評価。
５：つぶれない
４：ほとんどつぶれない
３：つぶれるが元に戻る
２：つぶれる
１：かたまっていない
・キュアー性：成形後、成形物にべたつきの有無で評価。
○：無、△：僅かにある、×：有[0001]
BACKGROUND OF THE INVENTION
  The present inventionFor automobiles and shipsImpregnating composition for interior material andFor automobiles and shipsThe present invention relates to a method for manufacturing an interior material.
[0002]
[Prior art]
  As the interior material, it is manufactured using a skin material, a back surface material, a core material, a reinforcing material, an adhesive, an impregnation agent, and other synthetic resins. For example, in JP-A-6-210786, as an interior material, from a base material having moldability, a fiber layer laminated on both sides or one side of the base material, and a skin material attached to the fiber layer shape The fiber layer is characterized by containing a thermoplastic fiber and / or a thermoplastic resin binder having a melting point lower than the molding temperature of the substrate. In this publication, polyurethane foam is impregnated with diisocyanate as a base material, and glass fiber is used as a reinforcing material. In JP-A-7-132573, as an interior material, a base material such as a raised cloth is composed of a polyurethane microporous layer, a polyurethane adhesive layer, a polyurethane skin layer, and the like.
[0003]
[Problems to be solved by the present invention]
  However, it can be obtained by the conventional method like thisFor automobiles and shipsInterior materials take a long time to mold, so productivity is reduced,For automobiles and shipsSince there are problems such as low hardness of the interior material, improvement is desired. With such performanceFor automobiles and shipsNo impregnating composition for interior materials has been obtained so far.
[0004]
  As a result of intensive research and study to improve the conventional problems, the present inventors,For automobiles and shipsThe present inventors have found that the above problems can be improved by using a composition comprising a polyisocyanate and a specific additive as an impregnating agent composition for interior materials, and reached the present invention.
[0005]
[Means for Solving the Problems]
  That is, the present invention comprises a polyisocyanate (A), a foam stabilizer (B), and an antifoaming agent (C), wherein (A) contains polymeric MDI or a derivative thereof,For automobiles and shipsAn impregnating composition for interior materials.
[0006]
  The present invention also provides the porous substrate with the above-mentionedFor automobiles and shipsAfter impregnating the impregnating agent composition for interior material, the catalyst or the catalyst and water are sprayed and thermocompression bonded at 85 to 150 ° C. for 10 to 150 seconds.For automobiles and shipsIt is a manufacturing method of interior material.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
  Of the present inventionFor automobiles and shipsThe polyisocyanate (A) used in the impregnating agent composition for interior materials is polymeric MDI, isocyanurate-modified polyisocyanate of polymeric MDI, an isocyanate group obtained by reacting the polymeric MDI polyisocyanate with an active hydrogen group-containing compound. It contains a terminal prepolymer.
[0008]
  In the present invention, “polymeric MDI” means an organic isocyanate compound having a different degree of condensation obtained by converting an amino group into an isocyanate group by phosgenation or the like of a condensation mixture (polyamine) obtained by a condensation reaction of aniline and formalin. The composition of the polymeric MDI finally obtained can be changed by changing the raw material composition ratio and reaction conditions during the condensation. The polymeric MDI used in the present invention has different numbers of reaction liquids after conversion to isocyanate groups, or removal of the solvent from the reaction liquids, or bottoms obtained by distilling and separating part of the MDI, reaction conditions and separation conditions, etc. It may be a mixture of seeds. Further, a part of the isocyanate group may be modified to biuret, allophanate, carbodiimide, oxazolidone, amide, imide or the like. Polymeric MDI contains diphenylmethane diisocyanate (hereinafter abbreviated as MDI) having two benzene rings and two isocyanate groups.
[0009]
  The polymeric MDI used in the present invention has an MDI content of 1 to 80% by mass, and other than 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as 4,4'-MDI) in the MDI in the polymeric MDI. The isomer content is preferably 0.1 to 70% by mass. When the MDI content of the polymeric MDI is too small, the viscosity of the impregnating composition becomes high, and the handleability tends to decrease. Also obtained if the MDI content is too highFor automobiles and shipsThe strength of the interior material tends to decrease. If the content of isomers other than 4,4'-MDI of MDI is too small, the storage stability in winter of the impregnating composition tends to be lowered. When the content of isomers other than 4,4′-MDI is too large, the thermocompression bonding time becomes long and the productivity tends to decrease. The MDI content of polymeric MDI and the isomer composition ratio of MDI can be determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography or gas chromatography.
[0010]
  You can also getFor automobiles and shipsIn view of storage stability and reactivity of the impregnating composition for interior materials, the acidity of the polymeric MDI used is preferably 0.001 to 0.2% by mass, more preferably 0.003 to 0.15% by mass. . When the acidity is less than 0.001%, the impregnating composition tends to thicken during storage, and when it exceeds 0.2%, the thermocompression bonding time becomes long and the productivity tends to decrease.
[0011]
  The “acidity” is a value obtained by converting an acid component that reacts with alcohol at room temperature and liberated into hydrogen chloride, and is a value measured by JIS K1603 (1985).
[0012]
  Moreover, the average functional group number of the polymeric MDI used for this invention is 2.3 or more, Preferably the functional group number is 2.3-3.1. The isocyanate content is 28 to 33% by mass, preferably 28.5 to 32.5% by mass.
[0013]
  Furthermore, the isocyanurate-modified polyisocyanate of the polymeric MDI can also be used.
[0014]
  Isocyanuration can be obtained by adding an isocyanuration catalyst and a co-catalyst to polymeric MDI and reacting at a temperature of 100 ° C. or lower, preferably 20 to 70 ° C. When the reaction temperature is 100 ° C. or higher, an isocyanurate polymer is likely to be formed, so that compatibility may be reduced or gelation may occur. By selecting a suitable amount of isocyanuration catalyst and reaction temperature, the isocyanuration reaction proceeds sequentially, and therefore can be easily carried out by a conventional production apparatus. Further, the content and viscosity of the isocyanurate ring to be obtained can be freely adjusted by adjusting the isocyanate content at the time of stopping the reaction. The isocyanurate-modified polyisocyanate used in the present invention is preferably 20% by mass or less, preferably 0.5 to 10% by mass of the isocyanurate group of all isocyanate groups before isocyanuration.
[0015]
  As a catalyst for the isocyanuration reaction, 2,4,6, -tris (dimethylaminomethyl) phenol, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-triazine, a mixture of potassium octylate and diethylene glycol A mixture of tertiary amine, potassium octylate and diethylene glycol, potassium phenolate, phenolate such as sodium methoxide, alcoholate, more particularly effective 2,4,6-tris (dimethylaminomethyl) phenol, 2,4-bis ( Dimethylolaminomethyl) phenol, 2,6-di-t-butyl-4-dimethylaminotrimethylsilanephenol, triethylamine diazabicycloundecene, lead naphthenate, lead octenoate, etc. Use of Isocyanuration Catalyst The amount of its catalyst It varies depending activity, but is preferably 0.0001 to 2 mass% of the reaction system.
[0016]
  Examples of the co-catalyst for the isocyanuration reaction include phosphites and phosphates. Examples of phosphites include phosphite diesters and phosphite triesters. Examples of phosphorous acid diesters include dilauryl hydrogen phosphite and diphenyl hydrogen phosphite. Examples of phosphorous acid triesters include triethyl phosphite, triptyl phosphite, tris (β-chloroethyl) phosphate, tris (β-chloropropyl) phosphate, and the like. The amount of the cocatalyst used is preferably 0.0001 to 10% by mass of the reaction system.
[0017]
  In order to stop the isocyanuration reaction, it is preferable to use an isocyanuration stopper. An acidic compound can be used as this terminator. For example, phosphoric acid, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, triphenyl phosphate, triftyl phosphate, p-toluenesulfonic acid, methyl p-toluenesulfonate, xylenesulfonic acid, benzenesulfonic acid Methanesulfonic acid, alkylbenzenesulfonic acid, dinaphthalene monosulfonic acid, dinaphthalenedisulfonic acid, dinonylnaphthalene monosulfonic acid, benzoyl chloride, acetyl chloride, and the like, and the like. The terminator for isocyanuration is preferably used in an amount of 0.3 to 5.0 times equivalent, more preferably 0.8 to 3.0 times equivalent to the amount of the catalyst. By adding an isocyanurate-forming terminator to the reaction system, the reaction product can be stabilized without turbidity of the reaction solution. Also, when using phosphoric acid as a terminator,For automobiles and shipsThe flame retardancy of the interior material can be improved.
[0018]
  In the present invention, an isocyanate group-terminated prepolymer obtained by reacting polymeric MDI and / or isocyanurate-modified polymeric MDI with an active hydrogen group-containing compound can be used.
[0019]
  Examples of the active hydrogen group-containing compound used to obtain the isocyanate group-terminated prepolymer include low-molecular monools, low-molecular polyols, low-molecular amino alcohols, low-molecular monoamines, low-molecular polyamines, and hydroxyl-containing polyethers. , Hydroxyl group-containing polyesters, hydroxyl group-containing polycarbonates and the like. The active hydrogen group-containing compounds can be used alone or in combination of two or more.
[0020]
  Examples of the low-molecular monools include methanol, ethanol, propanol, butanol, octanol, and lauryl alcohol.
[0021]
  Low molecular polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1, Examples include 4-butanediol, 1,6-hexanediol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, glycerin, trimethylolpropane, pentaerythritol, and diglycerin.
[0022]
  Low molecular amino alcohols include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N- (β-aminoethyl) ethanolamine, N- (β-aminoethyl) isopropanolamine and the like can be mentioned.
[0023]
  Examples of the low molecular monoamines include ethylamine, propylamine, butylamine, diethylamine, dibutylamine, aniline, N-methylaniline and the like.
[0024]
  Low molecular weight polyamines include tetramethylenediamine, hexamethylenediamine, tolylenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, diethyltriamine, dibutyltriamine, And propylene triamine.
[0025]
  Hydroxyl-containing polyethers include low-molecular monools, low-molecular polyols, low-molecular amino alcohols, low-molecular monoamines, low-molecular polyamines, phenol, alkyl-substituted phenols, bisphenol A, and thiols alone or as a mixture. As an initiator, an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide, an epoxide such as styrene oxide, or a cyclic ether such as tetrahydrofuran can be used alone or in combination, and can be obtained by addition polymerization by a known method. Can be mentioned.
[0026]
  Hydroxyl-containing polyesters and hydroxyl-containing polyamide-esters include the low molecular polyols, low molecular amino alcohols, low molecular polyamines, alone or in mixture, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid. , Azelaic acid, sebacic acid, maleic acid, fumaric acid, o-phthalic acid, i-phthalic acid, t-phthalic acid, and polycarboxylic acids such as trimellitic acid obtained by polycondensation by known methods Can be mentioned.
[0027]
  As the hydroxyl group-containing polycarbonates, the above low molecular polyols are used alone or as a mixture, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, diaryl carbonates such as diphenyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, phosgene and the like. And those obtained by polycondensation by the above method.
[0028]
  Of these active hydrogen group-containing compounds, polyols are preferred in view of the viscosity of the resulting polyisocyanate, and low molecular polyols are most preferred.
[0029]
  In the present invention, a polyisocyanate other than the above-described polymeric MDI system can be used as necessary. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene -1,3-diisocyanate, tetramethylxylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and other aromatic diisocyanates, tetramethylene diisocyanate, hexamethylene diisocyanate, 3-methyl-1,5-pentane diisocyanate, lysine diisocyanate, etc. Aliphatic diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate Alicyclic diisocyanates, and the like of. Also, urethanized products, urea compounds, allophanate compounds, biuret compounds, carbodiimidides, uretoniminates, uretdione compounds, isocyanurate compounds obtained by reacting these polymeric substances and these isocyanates with the aforementioned active hydrogen group-containing compounds. Etc. Furthermore, the mixture of these 2 or more types is mentioned.
[0030]
  The foam stabilizer (B) used in the present invention is preferably a heat-resistant silicone foam stabilizer, for example, L-5340, SZ-1642 manufactured by Nihon Unicar, B-8451 manufactured by Goldschmidt, Toray Dow Corning Silicone. Examples thereof include SF-2964, SF-2936F, and the like. The usage-amount of such surfactant is 0.0001-5 mass% with respect to 100 mass parts of polyisocyanate compositions.
[0031]
  The antifoaming agent (C) used in the present invention is preferably a heat-resistant silicone-based antifoaming agent, such as KF-6001, KF-96 from Shin-Etsu Chemical, TSF-451, TSF-4751 from GE Toshiba Silicone. Etc. The usage-amount of such an antifoamer is 0.0001-2 mass% with respect to 100 mass parts of polyisocyanate compositions.
[0032]
  The foam stabilizer used in the present invention improves the stability of the liquid and is stable with no generation of crystals, precipitates, etc. even in cold regions of −5 ° C. or lower. Moreover, the compatibility of the whole system can be improved, the balance of the whole composition can be balanced, the reactivity can be improved, and the physical properties such as dimensional stability and flame retardancy of the resulting interior material can be improved. In addition, since the antifoaming agent eliminates the foam in the polyisocyanate composition in the production process, the base material can be impregnated with the polyisocyanate more uniformly and obtained.For automobiles and shipsThis leads to higher strength interior materials.
[0033]
  If necessary, the present inventionFor automobiles and shipsA catalyst can be added to the impregnating agent composition for interior materials in order to adjust the reactivity. Examples of the catalyst include those generally known as transesterification catalysts, urethanization catalysts, blocked isocyanate dissociation catalysts, isocyanurate formation catalysts, and more specifically, dibutyltin dilaurate, stannous octoate, etc. Tin-based catalyst, triethylenediamine, triethylamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, N-methylmorpholine, 1, 2-dimethylimidazole, 1,5-diaza-bicyclo (4,3,0) nonene-5, 1,8-diazabicyclo (5,4,0) -undecene-7 (hereinafter abbreviated as DBU), these amines Various amine salt catalysts such as catalyst borane salt, DBU phenol salt, DBU octylate, DBU carbonate Magnesium naphthenate, lead naphthenate, zinc naphthenate, carboxylates such as potassium acetate, triethyl phosphine, trialkyl phosphines such as tribenzylphosphine, alkoxides such as sodium methoxide and the like. The amount added isFor automobiles and ships1 mass% or less is preferable with respect to the impregnating agent composition for interior materials.
[0034]
  In addition, the present inventionFor automobiles and shipsThe interior material impregnating composition is added with various known additives and auxiliaries such as antioxidants, UV absorbers, flame retardants, plasticizers, pigments / dyes, antibacterial agents / antifungal agents, etc. You can also
[0035]
  Of the present inventionFor automobiles and shipsIn addition to improving the strength of the porous base material as the impregnating agent, the interior material impregnating composition is used at the interface between these and the porous base material when, for example, a skin material, a back surface material, a reinforcing material, or the like is used. The effect as a binder is added. Moreover, when using fillers, such as a filler, the effect as these surface treating agents is added. That is,For automobiles and shipsWhen the skin material, the back surface material, the reinforcing material, and the filler are used in combination during the production of the interior material, it is only necessary to use the impregnating agent of the present invention, and it is not necessary to use a binder or a surface treatment agent.
[0036]
  Of the present inventionFor automobiles and shipsThe method for producing the interior material is the same as that described above for the porous substrate.For automobiles and shipsAfter impregnating the interior material impregnating agent composition, if necessary, a base material selected from a skin material, a back surface material, and a reinforcing material is placed on the upper surface and / or the lower surface of the base material, and then a catalyst or a catalyst and water Is sprayed and thermocompression bonded at 85 to 150 ° C. for 10 to 150 seconds.
[0037]
  The amount of catalyst sprayed is the catalyst alone.For automobiles and shipsThe amount of 1 to 20% by mass with respect to the impregnating agent composition for interior materials is preferred. When using water and catalyst togetherFor automobiles and ships2-80 mass% is preferable with respect to the impregnating agent composition for interior materials. The mass ratio of water / catalyst when water and the catalyst are used in combination is preferably 1/1 to 15/1. Examples of the catalyst include those described above.
[0038]
  continue,For automobiles and shipsThe porous substrate impregnated with the impregnating agent composition for interior material is subjected to thermocompression bonding. The conditions at this time are preferably temperature: 85 to 150 ° C. and time: 10 to 150 seconds, and particularly preferably temperature: 90 to 140 ° C. and time: 20 to 120 seconds. The pressure is preferably 0.1 to 10 MPa, particularly preferably 0.2 to 5 MPa.
[0039]
  In addition, after thermocompression bonding at a temperature lower than 85 ° C. (for example, 80 ° C.), by further aging at 30 to 70 ° C. for 0.5 to 48 hours,For automobiles and shipsInterior materials can be manufactured. However, thermocompression bonding at a low temperature is not preferable because it requires a sufficient aging step and is inferior in productivity.
[0040]
  The porous substrate used in the present invention may be anything as long as it has moldability by impregnating the impregnating composition and thermocompression bonding, such as cloth, paper, felt, wool, cotton, glass fiber, steel. Examples thereof include wool, resin fiber, hard foam plastic, soft foam plastic, and ribbon dead foam using a soft foam chip. In the present invention, a particularly preferable porous substrate has a density of 10 to 200 kg / m such as a slab foam cut product or a ribbon dead foam using a foam chip.^ThreeThis is a flexible polyurethane foam.
[0041]
  Obtained by the present inventionFor automobiles and shipsThe interior material is particularly excellent in initial hardness and overall rigidity, providing heat insulation, performance as a lightweight structural material, sound absorption, etc.Have.
[0042]
【The invention's effect】
  Of the present inventionFor automobiles and shipsThe impregnating composition for interior materials has a low viscosity, good permeability to the base material, excellent long-term storage stability at low and high temperatures, and good affinity with a porous base material,For automobiles and shipsWhen used as an interior material, an interior material having excellent hardness and rigidity can be obtained. In addition, by adopting a ribbon dead foam using a flexible polyurethane foam chip as a base material, it is possible to reduce the environmental burden and cost.
[0043]
【Example】
  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto. “%” In the examples is “% by mass” unless otherwise specified.
[0044]
[For automobiles and shipsProduction of impregnating composition for interior material]
Examples 1 to 4 and Comparative Example 2
  Into a reactor equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe, and a thermometer, the raw materials shown in Table 1 or Table 2 were charged, and then stirred at 40 ° C. for 1 hour.For automobiles and shipsImpregnating compositions for interior materials (NCO-1 to 4, 11) were obtained.
[0045]
Example 5
  A reactor similar to that in Example 1 was charged with 300 g of MDI (1) and heated to 45 ° C. Next, 6.3 g of 1,3-BD was charged and reacted at 60 ° C. for 2 hours. After the reaction, 400 g of P-MDI (1), 200 g of P-MDI (2) and 100 g of MDI (2) were charged and stirred at 40 ° C. for 1 hour.For automobiles and shipsAn impregnating composition for interior materials NCO-5 was obtained.
[0046]
Example 6
  A reactor equipped with a stirrer, a cooling tube, a nitrogen introducing tube, and a thermometer was charged with 200 g of P-MDI (7) and heated to 45 ° C. Next, 1.4 g of EDA was charged and reacted at 60 ° C. for 2 hours. After the reaction, 450 g of P-MDI (2), 100 g of P-MDI (6), 150 g of MDI (1) and 100 g of MDI (3) were charged and stirred at 40 ° C. for 1 hour.For automobiles and shipsAn impregnating composition for interior materials NCO-6 was obtained.
[0047]
Example 7
  A reactor similar to that in Example 1 was charged with 100 g of P-MDI (8) and heated to 45 ° C. Next, 0.2 g of K-54 was charged and heated to 60 ° C. to initiate an isocyanurate (trimerization) reaction. When the isocyanate content reached 29.0%, 0.13 g of RA-600 was charged to stop the reaction, and isocyanurate-modified polyisocyanate was obtained. Thereafter, 100 g of P-MDI (4), 550 g of P-MDI (6) and 250 g of MDI (2) were charged and stirred at 40 ° C. for 1 hour.For automobiles and shipsAn impregnating composition for interior materials NCO-7 was obtained.
[0048]
Example 8
  A reactor similar to that in Example 1 was charged with 100 g of P-MDI (8) and heated to 45 ° C. Next, 0.2 g of K-54 was charged and heated to 60 ° C. to initiate an isocyanurate (trimerization) reaction. When the isocyanate content reached 29.0%, 0.13 g of RA-600 was charged to stop the reaction, and isocyanurate-modified polyisocyanate was obtained. Next, 2.1 g of 1,3-BD was charged and reacted at 60 ° C. for 2 hours. Thereafter, 100 g of P-MDI (4), 550 g of P-MDI (6) and 250 g of MDI (2) were charged and stirred at 40 ° C. for 1 hour.For automobiles and shipsAn impregnating agent composition for interior materials NCO-8 was obtained.
[0049]
Example 9
  A reactor similar to that in Example 1 was charged with 100 g of P-MDI (8) and heated to 45 ° C. Next, 0.2 g of K-54 was charged and heated to 60 ° C. to initiate an isocyanurate (trimerization) reaction. When the isocyanate content reached 29.0%, 0.13 g of RA-600 was charged to stop the reaction, and isocyanurate-modified polyisocyanate was obtained. Next, 0.7 g of EDA was charged and reacted at 60 ° C. for 2 hours. Thereafter, 100 g of P-MDI (4), 550 g of P-MDI (6) and 250 g of MDI (2) were charged and stirred at 40 ° C. for 1 hour.For automobiles and shipsAn impregnating agent composition for interior materials NCO-9 was obtained.
[0050]
Comparative Example 1
  A reactor similar to that in Example 1 was charged with 150 g of MDI (1) and heated to 45 ° C. Next, 3.2 g of 1,3-BD was charged and reacted at 60 ° C. for 2 hours. Thereafter, 500 g of P-MDI (4), 250 g of P-MDI (5) and 100 g of MDI (2) were charged and stirred at 40 ° C. for 1 hour.For automobiles and shipsAn impregnating composition for interior materials NCO-10 was obtained.
[0051]
[Table 1]

[0052]
[Table 2]

[0053]
In Examples 1 to 9, Comparative Examples 1 and 2, and Tables 1 and 2
P-MDI (1): Polymeric MDI
                    Isocyanate content = 31.0%
                    MDI content = 39%
                    4,4′-MDI content in MDI = 98%
                    Acidity = 0.006%
P-MDI (2): Polymeric MDI
                    Isocyanate content = 31.5%
                    MDI content = 45%
                    4,4′-MDI content in MDI = 87%
                    Acidity = 0.006%
P-MDI (3): Polymeric MDI
                    Isocyanate content = 31.0%
                    MDI content = 43%
                    4,4′-MDI content in MDI = 96%
                    Acidity = 0.010%
P-MDI (4): Polymeric MDI
                    Isocyanate content = 29.5%
                    MDI content = 43%
                    4,4′-MDI content in MDI = 95%
                    Acidity = 0.015%
P-MDI (5): Polymeric MDI
                    Isocyanate content = 31.0%
                    MDI content = 34%
                    4,4′-MDI content in MDI = 75%
                    Acidity = 0.006%
P-MDI (6): Polymeric MDI
                    Isocyanate content = 30.1%
                    MDI content = 27%
                    4,4′-MDI content in MDI = 99.5%
                    Acidity = 0.008%
P-MDI (7): Polymeric MDI
                    Isocyanate content = 30.2%
                    MDI content = 35%
                    4,4′-MDI content in MDI = 86%
                    Acidity = 0.006%
P-MDI (8): Polymeric MDI
                    Isocyanate content = 31.0%
                    MDI content = 41%
                    4,4′-MDI content in MDI = 98.5%
                    Acidity = 0.006%
MDI (1): Diphenylmethane diisocyanate
                    4,4′-MDI content in MDI = 81%
                    Acidity = 0.006%
MDI (2): Diphenylmethane diisocyanate
                    4,4′-MDI content in MDI = 70%
                    Acidity = 0.006%
MDI (3): Diphenylmethane diisocyanate
                    4,4′-MDI content in MDI = 99%
                    Acidity = 0.006%
1,3-BD: 1,3-butanediol
EDA: Ethylenediamine
K-54: isocyanurate-forming catalyst
                    2,4,6-tris (dimethylaminomethyl) phenol
                    Air Products & Chemical
RA-600: isocyanurate terminator
                    Acid phosphate ester, manufactured by Toho Chemical Industry
SZ-1642: Silicone foam stabilizer, manufactured by Nihon Unicar
B-8451: Silicone foam stabilizer, manufactured by Gold Schmidt
L-5340: Silicone foam stabilizer, manufactured by Nippon Unicar
TSF-451: Silicon-based antifoaming agent, manufactured by GE Toshiba Silicone
KF-96: Silicone defoamer, manufactured by Shin-Etsu Chemical Co., Ltd.
TSF-4751: Silicon-based antifoaming agent, manufactured by GE Toshiba Silicone
KF-6001: Silicone defoamer, manufactured by Shin-Etsu Chemical
DBTDL: Dibutyltin dilaurate
U-CAT SA1: DBU phenol salt, manufactured by Air Products and Chemicals
[0054]
[For automobiles and shipsStorage stability of impregnating composition for interior materials)
  ObtainedFor automobiles and shipsWhen the impregnating agent composition for interior materials was stored at 30 ° C. and −5 ° C. for 1 month, all the results obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were obtained.For automobiles and shipsThe appearance and viscosity of the impregnating agent composition for interior materials did not change and were good results.
[0055]
[For automobiles and ships(Manufacture of interior materials)
  For automobiles and shipsTEDA L-33 (a diethylene glycol solution of triethylenediamine, manufactured by Air Products and Chemicals) was used as a catalyst to be sprayed when producing the interior material. The press molding conditions are as follows.
  Temperature: 120 ° C
  Time: 30 seconds
  Pressure: 10MPa
[0056]
Example 10
  Flexible polyurethane slab foam (density: 30 kg / m^Three200 mm in length, 100 mm in width, and 7 mm in thickness) were impregnated with NCO-1 (impregnation amount: 2.6 g), 1.6 g of the catalyst was sprayed, and molded with a press molding machine. The results are shown in Table 3.
[0057]
Examples 11 and 16, Comparative Example 3
  Molding was performed in the same manner as in Example 10 except that NCO-2, 7, 10 were used instead of NCO-1. The results are shown in Tables 3 and 4.
[0058]
Example 12
  Flexible polyurethane foam ribbon dead foam (density: 80 kg / m^Three200 mm in length, 100 mm in width, 7 mm in thickness) is impregnated with NCO-3 (impregnation amount: 2.6 g) and sprayed with 1.6 g of a mixture of water: catalyst = 9: 1 (mass ratio). Molded with a press molding machine. The results are shown in Table 3.
[0059]
Examples 13 and 17, Comparative Example 4
  Molding was performed in the same manner as in Example 12 except that NCO-4, 8, and 11 were used instead of NCO-3. The results are shown in Tables 3 and 4.
[0060]
Example 14
  Flexible polyurethane foam ribbon dead foam (density: 50 kg / m^Three200 mm in length, 100 mm in width, 7 mm in thickness) was impregnated with NCO-5 (impregnation amount: 2.6 g) and sprayed with 1.6 g of a mixed solution of water: catalyst = 9: 1 (mass ratio). Then, the nonwoven fabric was applied to the upper part and the lower part of the foam, and it shape | molded with the press molding machine. The results are shown in Table 3.
[0061]
Examples 15 and 18
  Molding was performed in the same manner as in Example 14 except that NCO-6 and 9 were used instead of NCO-5. The results are shown in Tables 3 and 4.
[0062]
[Table 3]

[0063]
[Table 4]

[0064]
In Tables 3 and 4
-Reactivity: Visual evaluation of the degree of deflection of the molded product immediately after molding.
    1: Isocyanate oozes from the molded product.
    2: The molded product is soft and large.
    3: Although the molded product has hardness, it bends.
    4: The molded product is hard and has little deflection.
    5: The molded product is hard and does not bend.
・ Moldability: Evaluated by the presence or absence of cancer in the molded product after molding.
    ○: None, △: Slight, ×: Existence
Appearance: Evaluated by the presence or absence of isocyanate exudation from the molded product after molding.
    ○: None, △: Slight, ×: Existence
・ Initial hardness: After molding, press the molded product with your finger and evaluate the degree of crushing.
    5: Not collapse
    4: Almost unbreakable
    3: Collapses but returns
    2: Collapse
    1: not clumped
-Cure property: After molding, the molded product is evaluated for stickiness.
    ○: None, △: Slight, ×: Existence

Claims (7)

An impregnating composition for automobile and marine interior materials, comprising a polyisocyanate (A), a foam stabilizer (B), and an antifoaming agent (C), wherein (A) contains polymeric MDI. An interior material for automobiles and ships , comprising a polyisocyanate (A), a foam stabilizer (B), and an antifoaming agent (C), wherein (A) contains an isocyanurate-modified polyisocyanate of polymeric MDI. Impregnating composition. It consists of polyisocyanate (A), foam stabilizer (B), and antifoaming agent (C), and (A) contains an isocyanate group-terminated prepolymer obtained by reacting polymeric MDI with an active hydrogen group-containing compound. An impregnating composition for automotive and marine interior materials characterized by the above. Isocyanate group terminal obtained by reacting polyisocyanate (A), foam stabilizer (B), defoamer (C), and (A) reacting with isocyanurate-modified polyisocyanate of polymeric MDI and active hydrogen group-containing compound. An impregnating composition for automotive and marine interior materials , comprising a prepolymer. The diphenylmethane diisocyanate content in the polymeric MDI is 1 to 80% by mass, and the isomer content other than 4,4′-diphenylmethane diisocyanate in the diphenylmethane diisocyanate is 0.1 to 70% by mass. The impregnating composition for automotive and marine interior materials according to any one of claims 1 to 4. After impregnating the porous base material with the impregnating agent composition for automobile or marine interior material according to any one of claims 1 to 5, the catalyst or the catalyst and water are sprayed, and 10 to 150 at 85 to 150 ° C. A method for producing automotive and marine interior materials , characterized by thermocompression bonding for 2 seconds. A porous base material is impregnated with the impregnating agent composition for automobile or marine interior material according to any one of claims 1 to 5, and after spraying a catalyst or a catalyst and water, the upper surface and / or the lower surface of the base material A method for producing an interior material for automobiles and ships , comprising installing a base material selected from a skin material, a back surface material, and a reinforcing material, and thermocompression bonding at 85 to 150 ° C for 10 to 150 seconds.